Insecticides



amed be. 11, 1945 INSECTICIDES George H. Law and John H. Purse, SouthCharleston, W. Va., assignors to Carbide and Carbon ChemicalsCorporation, a corporation of New York No Drawing. Application December5, 1942, Serial No. 467,998

13 Claims. (01.167-30) Our copending application Serial No. 308,950,filed December 13, 1939, of which the present applicationis acontinuation in-part, describes insecticides and insecticidalcompositions based on the toxicity to insects of five aliphaticsecondary amines, viz. di-n-hexyl amine, di-n-heptyl amine,

. cyclopentenyl n-hexyl amine, ,cyclopentenyl n- As is was advanced asthe preferred and most toxic substance.

We have now determined by extensive investigation of the insecticidalqualities of a wide variety of amines that an unexpectedly high degreeof toxicityto insects is possessed by a larger group of amines than wasproposed in our earlier application, and that, contrary to what waspreviously supposed, this high degree of toxicity is definitelycorrelated with the'chemical structure of the amines. Di-n-hexyl amine,di-n-heptyl amine and di-2-ethylhexyl amine are not included in thislarger group of amines for the reason that improved testing procedureshave not shown these substances to have the degree 01 toxicity which weassigned to them in our earlier application.

This invention accordingly is directed to insecticidal materials andinsecticide compositions which contain as an essential ingredient one ormore amines of the general type in which at least one ofthe substituentradicals, R, is a cyclopentenyl group,

nc-cntact insecticides; they maybe combined with insect activating incharacter.

solid substances for application as dusts or pow ders; or they may,where appropriate conditions prevail and'where their volatility underthose conditions will permit, be used in the vapor or gaseousstate asfumigants. These amines may be combined with each other and with othersubstances, such as those known to be insecticidal or As examples ofthese there may be mentioned the active principles of derris andpyrethrum, sulfur and its compounds, rotenone and the like.

Cyclopentenyl amines can .be made by reaction of cyclopentenyl chloridewith ammonia and with primary and secondary amines by conventionalmethods used for the preparation of amines generally.

All of the cyclopentenyl amines are liquids possessing the usual odor ofamines, and exhibiting the general characteristics common to amines. Thephysical properties of representative cyclopentenyl amines are givenbelow, and, for comparison, the properties of di-n-hexyl amine,di-Z-ethylhexyl amine and a cyclopentylamine are also given.

Table I Bolling Absolute Specitfic A ine in e graviy m .attfi'fig 27120Degree: Mm. l N-cyclopcntenyl 108 760 0. 2 N-cyclopentenyl N-butyl 50 80. -15 N-cyclopenteuylN-hexyl 10 0.844 4 N-cyclopentenylN-heptyl. 98 50.845 5, N-cyclopeutenyl N-Z-ethylberyl fiffififififlf. 87 3 0.850

m 6 flg l l o t i -1 90 1 0.850

N tenl N-cyclo- 14 0.920 8 N-cyclopentenyl -al methylbenzyl 1 0. 990 9N-eyclopentenyl N-(2,5-endomethylene-fi-methyl- Nhfilfllhydlggfillllfigin--- 123 4 0.948 10 co n y 54 -1.

3mg: ydrobenz'yl).-- us 2.6 0.919 11 N-cyclopentenyl N,, N-dibutyl n ufii 84 1. 5 0. 841 m aif? $3 128 0.5 0.826 13 N, il-dicyclopentenyl N- 1butyl h i a 97 3 0.9 0 14 N N-dicyclopen y i'athylhexyl 12s 1 0.889 l l'l t l Nz-etb l- 1 16 N N-di-n-heryi.- 11 N:N-di-2-ethylhexyl..--- 121 10.707

In order todetermine the insecticidal potency of these amines byprocedures that enable consistently reproducible and reliable results tobe obtained, they were tested in comparison with a reference materialcorresponding in potency to the Oflicial Test Insecticide of theNational Association of Insecticide and Disinfectant Manufacturers.

The apparatus used for the tests consists of a spray gun mounted on topof a, cylindrical spray tower which, in turn, rested on a basecontaining the insects to be treated. The tower was 36 inches tall withan inside diameter of 8 inches.

The test insect used wasthe common fly (Musca' domestica). In conductingeach test, approximately 50 flies, four to flve days old, were placed inthe apparatus andtreated with a spray of the material to be tested.After 24 hours, the

- number of flies dead and alive was determined.

The potency of the material is expressed as the percentile value of theaverage number of flies killed in four tests.

Each substance to be tested was dissolved in a highly refined kerosenefraction at a concentration of either 1000 or 2000 milligrams per 100,

milliliters of finished spray. The reference spray contained 100milligrams of pyrethins per 100 milliliters of spray. Each treatment wasreplicated twice on each of two different days. Equal volumes of all thesolutions tested were employed.

Under these testing conditions, the reference spray produced a mortalityof approximately 50% of the flies treated (average value 52% for testson each of seven difi'erent days, a total of 14 tests).

The following is a tabulation of the results of tests on ten-of thecyclopentenyl amines named in Table I:

Table II It is evident from Table II that the introduction 01 thecyclopentenyl group into amines of all classes brings to these amines aremarkable insecticidal potency. Moreover, the potency of the amines ofthis invention is directly attributable to the presence of theunsaturated obtained is a commonly used modification of the Feet-Gradymethod, and has been shown to give reliable and reproducible results. Itpossesses the advantages of requiring less space and fewer insects. Someof the cyclopentenyl amines of this invention have been tested by thePeel;-

as fA sprays.

While fly spray tests as described are considered the most reliable andrepresentative means of evaluating materials for insecticidal purposes,other tests under a variety of condi-,

tions employing several species of test insects have invariably shownthat the cyclopentenyl amines as a class possess unusually greatinsecticidal potency. Numerous members of this class have been testedand found to be enective to kill mosquito larva (Culex pipiens andCulea:quinquefasciatus) in water, as fumigants against confused flour beetles(Tribolium confusum), and rice weevils (Sitophilus oryzae), and ascontact insecticides against aphids (Aphis rumicis).

The use of the cyclopentenyl amines of this as defined by the appendedclaims.

cyclopentenyl group. This is shown by the fact i that N-cyclopentenylN-2-ethylhexyl amine (No. 3) produced 100% mortality in these tests,whereas the analogous compound in which the saturated cyclopentyl groupreplaggq, t e' f pentenyl group, No. ll producedi mortality of only 41%.It will be observed that the testing method described above diilers fromthe Feet-Grady the method by which the data of Table II were We claim: i

1. Insecticide compositionessentially containing N-cyclopentenylN-cyclohexyl amine.

2. Insecticide'composition essentially containing N-cyclopentenylN-2ethylhexyl amine.

3. Insecticide composition essentially containing N,N-dicyclopentenylN-2-ethylhexyl amine.

4. Method of-combatting insect pests which comprises subjecting them toN-cyclopentenyl N-cyclohexyl amine. 5. Method of combatting insect pestswhich comprises subjecting them to N-cyclopentenyl N-Z-ethylhexyl amine.

6. Method of combatting insect pests which comprises subjecting them toN,N-dicyclopentenyl N-2-ethylhexyl amine.

7. Insecticide composition comprising: an amine of the group consistingof primary, secondary and tertiary amines having at least onecyclopentenyl group attached directly to the amino nitrogen atom; and acarrier for said amine.

8. Insecticide composition comprising an oil and an amine of the groupconsisting of primary, secondary and tertiary amines having at least onecyclopentenyl group attached directly to the amino nitrogen atom. I

9. Insecticide composition comprising a kerosene fraction and an amineof the group consisting of primary, secondary and tertiary amines havingat least one cyclopentenyl group attached least one cyclopentenyl groupattached directlyto the amino nitrogen atom.

11. Method of combatting insect pests which comprises subjecting them toa composition comprising: an amine or the group consisting of primary,secondary and tertiary amines having at least One cyclopentenyl groupattached directly to the amino nitrogen atom; and a carrier for saidamine.

12, Method of combatting insect pests which comprises subjecting them toa composition comprising an oil and an amine of the group consisting ofprimary, secondary and tertiary amines 10 having at least onecyclopentenyl group attached directly to the amino nitrogen atom.

